Carbamate esters of 2-oxyimino-3-keto-1,4-diheterocyclics

ABSTRACT

Chemical compounds of the class of carbamate esters of 2oxyimino-3-keto-1,4-diheterocyclics, such as 2methylcarbamoyloxyimino-4-methyl-3-thiomorpholinone useful in controlling pests such as insects and nematodes.

United States Patent Bellina [451 May 13, 1975 CARBAMATE ESTERS OF2-OXYlMINO-3-KETO-l ,4- DIHETEROCYCLICS Russell F. Bellina, Claymont,Del.

E. l. du Pont de Nemours & Company, Wilmington, Del.

Filed: Oct. 25, 1973 Appl. No.: 409,667

Related US. Application Data Division of Ser. No. 171,388, Aug. I2,I97], Pat. No. 3,790,566.

Inventor:

Assignee:

[1.5. CI. 260/239.3 R; 424/275 Int. Cl. C07d 93/38; C07d 93/44 Field ofSearch 260/2393 R [56] References Cited UNITED STATES PATENTS 3,801,5714/l974 Reichel .i 260/2393 R Primary Examiner-Henry R. Jiles AssistantExaminerR0bert T. Bond [57] ABSTRACT 2 Claims, No Drawings 1 2 CARBAMATEESTERS OF The compounds of formula I are prepared by car-2-OXYIMINO-3-KETO-l,4-DIHETEROCYCLICS bamylating intermediate2-oxyimino-3-keto-l ,4- This is a division, of application Ser. No.171,388, diheterocyclics. The latter form a novel class of comfiled Aug.12, l97l. pounds of the formula:

BACKGROUND OF INVENTION 5 O Copending application Ser. No. 851,531 filedJuly 9, l 1969. discloses alkyl 1-carbamoyl-N-(substituted Mcarbamoyloxy)thioformimidates and their use as pesticides. The compoundsof the present invention are l structurally distinct from the compoundsof this earlier application.

SUMMARY OF INVENTION This invention relates to carbamate esters of 2-oxyimino-3-keto-l,4-diheterocyclics of the following wherein R and n aredefined as above for the compounds of formula I.

A further embodiment of the present invention involves a novel method ofpreparing the compounds of formula: formula 11 wherein al-alkoxycarbonylformhydroxamyl 1? chloride [Berichte 88, 133 (1955)] isreacted with an N C O N l aminothiol or aminothiolhydrohalide in thepresence of R3 base. CH2 )n DETAILED DESCRIPTION OF INVENTION wherein Ris hydrogen, alkyl of 1-6 carbon atoms, alkenyl of Preparation 3-4carbon atoms or alkynyl of 3-4 carbon atoms; The compounds of formula Iwherein both R and R R is hydrogen, alkyl of 1-3 carbon atoms or allyl;are hydrogen are prepared by allowing an appropriate R is hydrogen ormethyl; and 2-oXyimino-3-keto-1,4-diheterocyclic of formula II to n is2, 3 or 4. react with sodium cyanate and hydrochloric acid at lowPreferred because of ease of synthesis and higher actemperature. Thereaction is illustrated by equation tivity are those compounds offormula I where (A):

\f a0rij R E? )L (A) i NaNCO H01 NHBCON i-R (CH2 )n R is alkyl of 1-3carbon atoms or ally]; The compounds of formula I wherein only one of RR is hydrogen. alkyl of l-2 carbon atoms or allyl; and R is hydrogen areprepared by allowing an appro- R is hydrogen or methyl; and priateintermediate of formula [I to react with a substin is 2 or 3. tutedisocyanate in an inert solvent such as acetone or Most preferred becauseof highest activity are 2- acctonitrile. The reaction is illustrated byequation (B):

l? O HON N411 R mason -R (B) RZNCO trace "Dabco" 2 l 1 S- (C 2) ortriechylamine methylcarbamoyloxyimino-4-methyl-3- The compounds offormula I wherein neither R nor thiomorpholinone and2-methylcarbamoyloxyimino-4- R is hydrogen are prepared by allowing anappropriate a gjg gfizzz g t zgg I can exist in either or intermediateofformula 11 to react with sodium hydride both the y? or anti geometricisomers in a solvent such as dioxane and treating the resultingCompounds of formula I exhibit excellent e ti idal salt with asubstituted carbamoyl chloride. The reacactivity combined with a goodmargin of safety for host lion is illustrated y equation HON Na on 4 INCON -R R R NCCl R 1 3 s (CH2 plants and mammals. Thus, these compoundsare The intermediates of formula 11 are made by allowing highly usefulin protecting plants from predacious pests analkoxycarbonylformhydroxamyl chloride to react such as insects andnematodes. In particular these comwith an appropriate aminothiol oraminothiol hydrohapounds control a wide variety of arthropods undervarilide followed by the addition of the correct amount of ousconditions at relatively low dosages. base. The reaction is illustratedby equation (D):

if H Home-0002a; as (CH2 na 11c 1 HON l 1 Suitable bases in theillustrated reaction can be a tertiary amine such as triethylamine,pyridine, or an alkali metal base such as sodium hydroxide or sodiummethoxide. At least two equivalents of base should be employed in theillustrated reaction where a hydrohalide salt of aminothiol is used as areactant. If the free aminothiol is used one equivalent of base isusually adequate.

Pests Controlled The compounds of this invention control a wide varietyof arthropods under many different conditions at low dosages. They havebeen found to be essentially non injurious to plants at relatively highrates of appli cation. Arthropods controlled by the compounds of thisinvention include, but are not limited to: aphids such as Aphis fabae,Myzus persicae, Macrosiphum euphorbiae, and others; weevils such asAmhonomus grandis, Hypera poslica, Hypera punclata, and others;lepidopterous larvae such as Prodenia eridania, Heliothis Zea, Heliorhisvirescens, Petlinopliora gosxrypiella, Pieris rapae, Trichopl'usia ni,Plutella macul'ipcnnix, Manduca sexta, Pludz'a inrerpunctella; thripssuch as Scirtothrips c'irri, Frankliniella tririci, Chueloanuphothripsorchiaii, Thrips rubaci, and others; flies such as Musca domestica andSlomoxys calcitrans; mosquitoes such as Anopheles spp, Culex spp., andAedes spp.; tarnished plant bugs, Lygus spp. and other mirids',grasshoppers such as Melanoplus spp., Camnula spp., and others; tickssuch as Hoophilus spp., Dermatentor spp., and others; fleas such asCrenocephalus spp., Pule); spp., Xenopsylla spp., and others; lice suchas Pediculus spp., Linognathus spp., Bovicola spp., and others; thecotton stainer, Dysdercus suturellus; and mites such as Terranychusspp., Panrmychus ulmi, and others.

In addition many of the compounds of the invention also controlnematodes. Illustrative of nematodes controlled are: Meluidogyneincognita, root knot; Trichodorus spp. stubby root; Tylenchorhynchusclayrom', tobacco stunt; Xiphiriema spp.; dagger; Helicatylenchus spp.,spiral; Hoplolaimus spp., lance; Pratylenchus spp., lesion;Pararylenchus spp., pin; and Rolylenchulus renifor-mus, reniformnematodes.

Formulations Compositions of this invention suitable for practical usewill include one or more compounds of formula (I) and can includesurface-active agents, solid or liquid dilucnts and other materials asdesired to produce wettable powders, suspensions, emulsifiableconcentrates, dusts, pellets, solutions, granules, or high-strength compositions.

The surface-active agents or surfactants, as they are sometimes called,useful in the formulations of this invention act as wetting, dispersingand emulsifying agents which assist dispersion of the active material ina spray. Additionally, the surfactants act as spreaders which aid inobtaining even coverage of the surfaces to be protected from insects andother pests. The surfactants can include such anionic. non-ionic andcationic agents as have been used heretofore in pesticidal compositionsof similar type. A detailed list of such agents may be found inDetergents and Emulsifiers Annual," (John W. McCutcheon, lnc. i970).

+ base Anionic and non-ionic surfactants are preferred. Among theanionic surfactants, preferred ones are alkali and alkaline earth saltsof alkylarylsulfonic acids, such as dodecylbenzenesulfonates andalkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodiumlauryl sulfate, sodium N-methyl-N oleoyltaurate, sodium dodecyldiphenylether disulfonate and the oleic acid ester of sodium isethionate. Amongthe non-ionic surfactants, preferred ones include octylphenyl,nonylphenyl and dodecylphenyl polyethylene glycol ethers,polyoxyethylene derivatives of sorbitan fatty esters and long-chainalcohols and mercaptans, as well as polyoxyethylene esters of fattyacids.

Preferred dispersants are alkali and alkaline earth salts oflignosulfonic acids, salts of polymerized alkylarylsulfonates which aresold under the Daxad" and Darvan trademarks, as well as methylcellulose,polyvinyl alcohol and the like.

Surfactants can be used in compositions of this invention in amounts ofup to l5% by weight based on the total weight of the resultinginsecticidal composition.

The compositions can contain, with or without a surfactant, a finelydivided solid diluent such as natural silicates, cg, tale, sepiolite,pyrophyllite; clays, e.g., montmorillonite, kaolinite, attapulgite;diatomaceous earth, synthetic magnesium silicate, synthetic silicas,calcium silicate, calcium sulfate, calcium carbonate, calcium phosphate,and flours derived from natural sources such as walnut shell, redwood,cottonseed and the like. The finely divided solids can be used in thecompositions of this invention at a concentration of l to 98% by weightbased on the total weight of the resulting pesticidal composition.Preferred finely divided solid formulations are high-strengthcompositions and powders containing 2 to 25% of synthetic silica and to98% active ingredients; and wettable powders containing 5 to 75% activeingredients, I to 5% surfactants, the remainder being finely dividedsolid diluents.

Organic liquids which are suitable for the preparation of solutions,suspensions and emulsifiable concentrates of the compounds of thisinvention include alcohols, glycols, cellosolves, carbitols, ketones,esters, sulfamides, amides, paraffinic hydrocarbons, aromatichydrocarbons, and halogenated hydrocarbons. Solvent combinations inwhich water-miscible solvents are combined with water, are particularlyuseful. Ordi narily, solvent choice is dictated by the solubility of theactive compound to be used and whether a suspension or solution isdesired.

Powder and dust preparations can be made by blending the activeingredient, with or without surfactant, with finely divided solids suchas tales, natural clays, pyrophyllite, diatomaceous earth; flours suchas walnut shell, wheat, redwood, soya bean and cotton seed; or inorganicsubstances such as magnesium carbonate, calcium carbonate, calciumphosphate, sulfur and lime. The compositions are made by thoroughlyblending the active ingredient with the diluent and other additives.Usually a grinding step, as in a hammer mill or fluid energy mill, isincluded. The particles in powder and dust preparations are preferablyless than 50 microns in average diameter.

Preferred wettable powder formulations will contain 40% or more activeingredient together with sufficient surfactant and inert diluent topermit dispersion in water for spray application.

Suspension formulations can be made in water or in organic solvents, orin mixtures of water and watermiscible organic solvents, in which theactive ingredient is insoluble and remains suspended. They are preparedby mixing and sandgrinding a slurry of insoluble active ingredient inthe presence of dispersing agents to obtain a concentrated slurry ofvery finely-divided particles in which the active ingredient issubstantially all below microns in size. Preferred carriers includealiphatic, aromatic and chlorinated hydrocarbons, and vegetable andanimal oils. Surfactants, viscosity control agents, anti-microbialagents and other modifiers may be used.

Solution formulations contain 20 to 50% active ingredient and 50 to 80%solvent or solvent-surfactant combinations. Preferred solvents aremethanol, dimethyl formamide, Cellosolve," aqueous mixtures of thesesolvents, isophorone and combinations of any of these. Other solventsinclude ketones, esters, and ethers. Solutions are prepared by stirringthe combined ingredients; in some cases warming may speed solution andin others cooling or pressure may be required to prevent evaporation ofthe solvent.

Emulsifiable concentrates are usually solutions or suspensions of activematerial in non-water-miscible solvents together with surfactants.Suitable surfactants are those anionic or non-ionic agents known to theart as emulsifying agents. Such compounds can be found listed by J. W.McCutcheon in Detergents and Emulsifiers Annual" (1970) by John W.McCutcheon, lnc. Emulsifying agents most suitable for the compositionsof this invention are alkylaryl polyethoxy alcohols, alkyl and alkylarylpolyether alcohols, polyoxyethylene sorbitol or sorbitan fatty acidesters, polyethylene glycol fatty esters, fatty alkylol amidecondensates, amine salts of fatty alcohol sulfates plus long chainalcohols, oil soluble petroleum sulfonates, alkylphenoxy polyethoxyphosphates and alkyloxy polyethoxy phosphate esters. Such emulsifyingagents will comprise from about 3 to weight percent of the totalcomposition.

Thus, emulsifiable compositions of the present invention will consist offrom about 25 to 50 weight percent active material, about 40 to 72weight percent carrier liquid, and to weight percent emulsifier, asthese terms are defined and used above.

Formulations in the form of granules are physically stable, particulatecompositions containing a compound of formula (I) which adheres to or isdistributed through a basic matrix of a coherent, inert carrier withmacroscopic dimensions. In order to aid leaching of the activeingredient from the granule, a surfactant can be present.

Suitable carriers are preferably of mineral origin such as naturalclays, some pyrophyllites, vermiculite and ground corn cobs. Suitablesurfactants are anionic or non-ionic.

For the granule compositions of this invention, most suitable carriersare of two types. The first are porous, absorptive, preformed granules,such as preformed and screened granular attapulgite or heat expanded,granular, screened vermiculite. On such preformed granules, an organicor aqueous solution of the active agent can be sprayed and will beabsorbed at concentrations up to 25 weight percent of the total weight.

Preformed granules can also be treated with a melt of active ingredientif the active ingredients melting point is sufficiently below itsdecomposition temperature. When this means of application is used, theactive ingredient in a very finely divided form is deposited on thesurface of the granules such as by tumbling in a mixer. The finelydivided active agent can if desired contain minor amounts of diluentssuch as synthetic silicas, natural clays and surface active agents.After the active agent is distributed on the granules the granules areheated to above the melting point of the active agent preferably whiletumbling is continued. The granules are then cooled and contain activeingredient within as well as fixed on their surfaces.

The second type of carrier suitable for granules is initially in apowder form. Powdered kaolin clays, hydrated attapulgite or bentoniteclays such as sodium, calcium and magnesium bentonite are blended withthe active ingredient and the mixtures are then granulated or pelletizedby conventional means. Water soluble salts can be included in thecompositions to aid in disintegration of the granules and pellets in thepresence of moisture. Such granules or pellets can be made containing 25to 50 weight percent of active ingredient, but more frequently aconcentration of 5 to l0 percent is preferred for optimum distribution.Such granular compositions are most useful in a size range of 15 to 60mesh (U.S.S.), i.e. 0.25 to L4 millimeters.

Additional modifiers can be used to advantage in the compositions ofthis invention. Thus, although the compounds of formula (I) are quitestable under most conditions, the use of a desiccant, buffering agent ormaterials such as urea, which inactive catalytic sites on diluentparticles can prove desirable. Additives which will inhibit corrosion,reduce foam, reduce caking and increase flocculation can also be used.

The compounds of this invention can be mixed with fungicides,bactericides, other acaracides, other nematicides, other insecticides orstill other biologically active compounds in order to achieve desiredresults with a minimum expenditure of time, effort and material. Amountsof these biologically active materials added for each part by weight ofthe compounds of this invention may vary from 0.025 to l0 parts byweight. Suitable agents of this type are well known to those skilled inthe art. Some are listed below:

a. fungicides tetramethyl thiuram disulfide (thiuram) n-dodecylguanidineacetate (dodine) manganese ethylenebisdithiocarbamate (maneb)l,4-dichloro-2,S-dimethoxybenzene (chloroneb) methyll-(butylcarbamoyl)-2- benzimidazolecarbamate (benomyl)N-trichloromethylthiotetrahydrophthalimide tan)N-trichloromethylthiophthalimide (folpet) b. bactericides tribasiccopper sulfate streptomycin sulfate c. acaricides senecioic acid, esterwith dinitrophenol (Morocide") 6-methyl-l ,3-dithiolol2,3-B]quinoxolin-2-one (Morestan") ethyl 4,4-dichlorobenzilate(Chlorobenzilate) 1,l -bis( p-chlorophenyl)-2,2,2-trichloroethane(Kelthane) bis(pentachloro-2,4-cyclopentadien-lyl) (Pentac) d.nematicides S-methyl l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate S-methyll-carbamoyl-N-(methylcarbamoyloxy)thioformimidate (cap- 2-sec-butyl-4,6-

7 N-isopropylphosphoramidic acid, O-ethyl-O-[4-(methylthioymtolylldiester (Nemacur) e. insecticides methyl carbamicacid, ester with oxime of Z-methyl- 2-methylthiolpropionaldehyde (Temik)3-hydroxy-N-methylcrotonamide (dimethylphosphate) ester (Azodrin) methylcarbarnic acid, ester with 2,3-dihydro-2,2-

dimethyl-I-benzofuranol (Furadan)O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid,O',O'-dimethyl ester (Gardona) 2-mercaptosuccinic acid, diethyl ester,S-ester with thionophosphoric acid, dimethyl ester (Malathion)phosphorothioic acid, 0,0-dimethyl, O-pnitrophenyl ester (methylparathion) methyl carbamic acid, ester with a-naphthol (Sevin) methylO-(methylcarbamoyl)thiolacetohydroxamate (methomyl) Application To beeffective the compounds of formula (I) must be applied in an amountsufficient to exert the desired pesticidal action. The amounts requiredto give pest control action are governed by many variables such astemperature, time of year, moisture, type of application, formulation,pest species to be controlled, resistance, and many other factors. Thusit is not possible to state any one method or rate of application whichwould be generally satisfactory. It is possible, however, to describegenerally some of the various methods and rates of application forcertain areas of use and to which the compounds of formula (I) are bestsuited.

The compounds of this invention may be applied directly to the peststhemselves or to areas visited by or infested with pests. Thus they maybe applied to the foliage of plants, soil, seeds or other areas wherepests thrive or congregate.

a. Foliar Application When used to protect plants by application to thefoliage, typical use rates are in the range of 0.05 to 30 kg of activeingredient per hectare. Rates of 0.1 to kg/ha are preferred and rates of0.1 to 5 kg/ha are most preferred for reasons of convenience andeconomy. This type of application may need to be repeated at intervalsof from 2 days. b. Seed Treatment Typical use rates for application toseeds are in the range of 006 gram to 3 kg of the active compound ofthis invention per 100 kg of seed. Preferred rates are in the range of0.6 to 600 grams per l00 kg of seed. Such treatment rates protect theseed during storage and shipping, and also serve to protect the seed andseedling from attack by insects, mites, or nematodes after planting.

c. Soil Application Quantities of from 0.1 to 50 kg/ha are generallyadequate for treating soil in which seeds are to be planted or in whichplants are growing. Preferred rates of application are in the range of0.3 to 20 kg/ha. These rates may be applied broadcast or in a bandcentered on the row for protection from soil pests.

d. Surface Application The compounds may be applied to the floors andwalls of structures such as warehouses, stores, recreation buildings,factories, homes, and animal shelters for control of arthropods whichattack or annoy people or domestic animals. Applications may be repeatedas needed.

The following examples are provided to further illustrate the invention.References to parts or percentages are by weight unless otherwisespecified.

EXAMPLE I Z-Carbamoyloxyimino-3-thiomorpholinone Part A To a mixture of69 parts of l-ethoxycarbonylformhydroxamyl chloride and 50 parts ofwater at 20C. was added over 3-5 minutes 2-aminoethanethiolhydrochloride. The reaction was cooled to about 0C. at which point asolution of 3.7 parts of sodium hydroxide in 46 parts of water was addeddropwise over 2 hours until the pH reaches 7.0. The crystalline productwas recrystallized from water furnishing white crystals of2-oxyimino-3-thiomorpholinone, m.p. 248-250.

Part B To a slurry of 7.3 parts of 2-oxyimino-3- thiomorpholinone in lOOparts of water at 0-l0 can be added slowly and simultaneously overseveral hours, 3.3 parts of sodium cyanate and 5 parts of concentratedhydrochloric acid. The product can be extracted with an organic solventsuch as ethyl acetate, dried over anhydrous magnesium sulfate andevaporated under reduced pressure to furnish 2-carbamoyloxyimino-3-thiomorpholinone.

In a similar manner, the aminothiol named on any line in Table 1 below(or its hydrochloride salt) can be substituted for the2-aminoethanethiol hydrochloride in Part A of Example 1 above to give a2-oxyimino-3- keto-l,4-diheterocycle intermediate which when treatedaccording to the procedure of Part B will give the Product named on thesame line of the table.

TABLE I Aminothiol Product -N-rnethylam inoethanethiol-N-hexylaminoethanethiol -N-isopropylaminoethanethiol-N-allylaminoethanethiol -N-( 2-butenyl)aminoethanethiol-N-proparglyarninoethanethiol 2-N-( 2-butynyl)aminoethanethiolZ-N-ethylaminoethanethiol 3-N-ethylaminopropanethiol2-N-methylaminopropanethiol NNNNNN Z-(N-methylamino )butanethiolZ-aminobutanethiol 2-(N-butylamino)butanethiol 2-( N-t-butylamino)ethanethiol 9 10 EXAMPLE 2 EXAMPLE 42-Methylcarbamoyloxyimino-4-methyl-3-2-Allylcarbamoyloxyimino-3-thiomorpholinone thiomorpholinone To a slurryof 1.9 parts of 2-oxyimino-3- Part A thiomorpholinone (described inExample I, Part A) in To 12.6 parts of 2N-methylaminoethanethiol hydro20 parts of acetone containing 3 drops of triethylamine chloride in 100parts of methanol was added 15.2 parts was one F Pans 0f all)" ofl-ethoxycarbonylformhydroxamyl chloride in one l reacuo at roomtemperature F portion Triethylamine (202 parts) was then added night,then chilled to 1 0 C and filtered. The crystall ne dropwise at aboutuntil the pH of the reaction product was recrystallized from ethylacetate to furnlsh reached and became stabilized at 7.0. The reactionwas '9 of zanylcaTamoyloxylmmo3' then allowed to stand overnight, wasevaporated and thlomorpholmone' -1 treated with hot acetonitrile. Afterthe acetonitrile was EXAMPLE 5 cooled, the triethylamine hydrochloridewas filtered and the filtrate stripped to furnish a viscous oil which 15gg zii ggzngi crystallized on standing. The crystals of 2-oxyimino-4- Toa Bluff of 1 6 arts of 2 0X imino 4 meth 3 methyl-3-thiomorpholinonewere washed with cold h f y 3 water and recrystallized from acetonitrilewhich pro lomorp cimone 9 parts 0 acietone .comammg duced white needlfisp 228L229? drops of trlethylamine was added in portion 1.1 parts Thereaction was run alternatively in the following Df lsocyanate'. Thereacuon was Sun-ed at mom manner. To a solution of 7.6 p of ltemperature overmght and evaporated under reducedethoxycarbonylformhydroxyamyl chloride and 4.5 pressure on a hot i bathto furnish L7 parts. of 2' parts of Z-N-methylaminoethanethiol in 100parts of l "T' "l ;'B methanol which had been standing at room temperaasf i 15639 T ture for 2 hours was added dropwise with stirring 5.1 332ZFJE$TEZ ig g fi? parts of triethylamine. The solution was then refluxedcmfl 0 an on a steam bath for 1 hour and allowed to slowly evaporate.The large needle-like crystals of 2-oxyimino-4- Lmethyl-3-thiomorpholinone which formed were (NHCO) washed with icewater, mip. 228229.5C.

B failed to crystallize.

To a slurry of l part of 2-oxyimino-4-methyl-3 EXAMPLE 6thiomorpholinone in 25 parts of anhydrous acetonitrile I containing atrace of Dabco was added in one por-ZMethylcarbamoyloxylmmo3thlomol'phohmf'n? tion 043 parts of methylisocyanate after which the re- T a Slurry of 3 Parts of action wasstirred overnight. The reaction was then thlomol'llholmone Prepareddlreclefj Example l chilled to and the product Part A, m 30 partsacetonitrile conta ning a catalyticmethylcarbamoyloxyimino-4-methyl-2,3-thiomorpho amount ofDabco was addeddropwise for 5 mlnutes linedione was filtered and recrystallized from 50parts 40 at m emperature l of l' lsocyfmate' of ethylacetate/acetonitrile, 5/1 to afford white crys- The m'ldly exothermlcrcacuon was Sun-ed :h tals, 146448.50. heating for 6 hours. TheZ-methylcarbamoyloxyimino- EXAMPLE 3 3thiomorph0lmed1one was thenfiltered and recrystallized from n-butanol/acetonitrile, 10/1, whichfur- 2-Methylcarbamoyloxyimino-4-methyltetrahydro-l ,4- i h d hicrystals, m.p. l68l70. thiazepin'3-0ne In a similar manner, the2-oxyimino-3-keto-l,4-

By t e Su tut of Z-N-methyIaminoethanethio 0f diheterocyclic and theisocyanate named on any line in Example 2 ith a equi en amount of Tablell below can be substituted for the 2-oxyimino-3-methylaminopropanethiol, ne Can similarly tain keto-l ,4-diheterocyclicsand isocyanates, respectively,methylcarbamoyloxyimino-4-methyltetrahydro-l ,4 utilized in Examples 2 6to give the Product" named thiazepin-3-one. on the same line in thetable.

TABLE ll 2 Oxyimino-3-keto l ,4-diheterocycle lsocyanate Productloxyimino-Lmelhyl-B-thiomorpholinone 2-0xyimino-4hexyl-3thiomorpholinone2-oxyimino-4 is0propyl3-thiomorpholinone2-oxyimin0-4-allyl-3-lhiomoprholinone 2oxyimino-4-(2-butenyl)3-thiomorethyl isocyanate methyl isocyanate propyl isocyanatcmethyl isocyanate allyl isocyanate 2-ethylcarbamoyloxyimin0-4methyl-3thiomorpholinone Z-methylcarbamoyloxyiminwlhexyl-3-thiomorpholinoneZpropylcarbamoyloxyiminc-4-isopropyl-3-thi0morpholinoneZ-methylcarbamoyloxyiminc-4-allyl-3-thiomorpholinone2-allylcarbamoyloxyimino-4-( 2-butenyH-3-thiomorpholinone pholinoneZ-oxyiminoA-(propargyl)-3-thiomormethyl isocyanateZ-methylcarbamoyloXyimino4-(propargyll-3-thiomorpholinone pholinone2-oxyimin0-4( 2-butynyll-3'thiomorethyl isocyanate2-ethylcarbamoyloxyiminoAJ 2-butynyl)-3-thiomor pholinone pholinone2-oxyimino-4-ethyl-3-thiomorpholinone 2-oxyimino-4-ethyltetrahydrol ,4

thiazepin-3 one 2 oxyimino-4-methyltetrahydro'4H- l ,4-

thiazocin-3-one 2-oxyimino-tetrahydro-4H-l ,4-thiazocin 3-oneZ-oxyimino-4-butyl-tetrahydro-4H-l .4-

thiazocin-3-onc 2-oxyimino-4-(t-butyl)-3-thiomorphol inone allylisocyanate methyl isocyanatc methyl isocyanatc ethyl isocyanate allylisocyanate methyl isocyanate2-allylcarbamoyloxyimino-4-ethyl-3-thiomorph0linoneZ-methylcarbamoyloxyimino-4-ethyltetrahydro-1,4-

thiazepin-3-one 2-methylcarhamoyloxyimino-4-methyltctrahyd ro- 4H-l,4-thiaz0cin-3-one 2-ethylcarbamoyloXyimino-tetrahydro-4H- l ,4-

thiazocin-lonc 2-allylcarbam0yloxyimino-4-butyl-tetrahydro- 4H-l .4thiazocin3-one 2-rnethylcarbamoyloxyimino-4-( t-butyl )-3-thiomorpholinone EXAMPLE 7 Dimethylcarbamoyloxyimino-4-methyl-3-thiomorpholinone To a solution of 1.6 parts of 2-oxyimino-4-methyl-3thiomorpholinone in 25 parts of anhydrous dioxane under nitrogen wasadded gradually 0.5 parts of 50% sodium hydride in mineral oil. Afterthe evolution of hydrogen subsided, the reaction was refluxed 1 hourafter which 1.2 parts of dimethylcarbamyl chloride was added in oneportion. The reaction was stirred for 30 minutes, refluxed 30 minutesand then allowed to stir at room temperature overnight. The resultingprecipitate was filtered, washed with ice water, and recrystallized fromacetonitrile to give 1 part ofdimethylcarbamoyloxyimino-4-methyl-3-thiomorpholinone, m.p. l80.5l83C.

In a similar fashion, the 2-oxyimino-3-keto-l,4- diheterocyclic andcarbamyl chloride named on any line in Table [11 below can besubstituted for the 2- oxyimino-4-methyl-3-thiomorpholinone anddimethylcarbamyl chloride, respectively, shown in Example 7 above tofurnish the Product named on the same line in the table.

TABLE I11 mm openings) before packaging.

Either of the above formulations can be added to water at the rate of 50grams active per 100 liters. The roots and lower stems of woody nurserystock infested with the lance nematode (HopIolaimus coronarus) can bedipped in this solution for approximately minutes and when so treatedand planted, will grow well.

EXAMPLE 9 Solution Z-rnethylcarbamoyloxyirninc-4-ethyl3 thiomorpholinoncdimethyl formamidc 75% EXAMPLE 10 Oil Suspension2-methylcarbamoyloxyimino4-methyl-3-thio morpholinonc polyoxyethylencsorhitol heptaoleate 8% synthetic fine silica 1% paraffinic hydrocarbonoil 61% The ingredients can be combined and sand milled to produceparticles essentially all below 5 microns.

This formulation so prepared can be applied to apple trees at aconcentration of 400 ppm active ingredient in water to runoff on a2-week schedule for the control 2-Oxyimino3-keto-1,4 dihctcrocycleCarbamyl Chloride Product 2-oxyimino-4-hcxyl-3thiomorpholinone2-oxyimino-4-isopropyl-3-thiomorph0- linone 2-oxyimino4-allyl-3thiomorpholinone chloride Z-oxyimino-4ethyltetrahydrol ,4thiazepin-3-one2-oxyimino-tetrahydro-4H-1,4-thiazocin- 3-one cZ-oxyimino-4-butyl-tetrahydro-4H- l ,4

thiazocin-3-one hloride chloride 2-oxyimino-4-(t-butyll-3-thiomorphodimethylcarbamyl chloride N-methyl-N-ethylcarbamylN-mcthyl-N-allylcarbamyl dimethylcarbamyl chloride dimethylcarbamylchloride N-methyl Nethylcarbamyl N -methyl-N-cthy1carbamy1N-methyl-N-ethylcarbamyl 2-dimethylcarbamoyloxyimino-4hexyl-3thiomorpholinone 2( Nmethyl-N-ethylcarbamoyloxyimino4isopropyl-3-thiomorpholinone 2( N-methyl N-allylcarbamoyloxyimino4-allyl-3-thiom0rpholinone 2( N-methyl-N-propylcarbamoyloxyimino)- 4-(2-butenyl )-3thiomorpholinone 2-dimethylcarbamoyloxyimino-4-( propargyl3-thiomorpholinone 2-dimethylcarbamoyloxyimino-4-(2butyny1)3-thiomorpholinone 2-dimethylcarbamoyloxyimino-4-ethyl-3-thiomorpholinone Z-dimcthylcarbamoyloxyimino-4-ethyltetrahydro 1,4-thiazepin-3 -one 2 dimethylcarbamoyloxyimino-4-methyltetrahydro-4H- l,4-thiazocin-3one 2 N'methyl-N-ethylcarbamoyloxyimino tetrahydro-AH- l,4-thiazocin-3-one linone chloride 4-( t-butyl 3-thiomorpholinoneEXAMPLE 8 of insects and mites. Treatment can be started shortly it i AHigh Smngm wmabic Powder after petal fall and continued to within 2weeks of 2-methylcarbamoyloxyimino-3-thiomorpholinone 80% 50 arvest'sodium alkylnaphthalenesulfonate 2% EXAMPLE I l low viscosity methylcellulose 2% diatomaceous earth 16% To prepare the above formulation theingredients can be thoroughly blended, passed through a hammer mill toproduce an average particle size under 40 microns, reblended, and siftedthrough a U.S.S. No. sieve (0.3 mm openings) before packaging.

To prepare the above formulation the ingredients can be thoroughlyblended, passed through an air mill to produce an average particle sizeunder 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve(0.3

The formulation of Example 10 can be dispersed in water and sprayed bymeans of a tractor-mounted sprayer at a rate of 1.5 kg of activeingredient in 50 liters of water per hectare of cotton. Applications canbe made on a weekly schedule starting when the plants are about 30 cmhigh and continuing until the plants are defoliated at the end of theseason. Excellent control of aphids, thrips, mites and boll weevils willbe obtained with this spray program.

EXAMPLE l2 Dust Z-methylcarbamoyloxyimino-3-thiomorpholinone 10%pyrugcnic silica 10% powdered talc In preparing the above formulation,the solid diluents can be dried by heating to 80C in dry air and thenallowed to cool. The active ingredient can then be blended with theinerts and hammer milled to produce an average particle size under 40microns.

The formulation thus prepared can be dusted on a field of potatoes on alO-day schedule at the rate of 0.5 kg/ha (active ingredient). Dustingshould be initiated when the plants are about 15 cm in height andcontinued until the vines become dry in the early fall. Such treatmentwill give excellent control of both aphids and Colorado potato beetle.

EXAMPLE 1 3 E 2 2-methylcarbamoyloxyiminc-4-allyl-3-thiomorpholinone l%alkyl naphthalene sulfonic acid, Na salt 1% 89% preformed granulardiatomaceous silica EXAMPLE l4 El i.Z-carbamoyloxyimino-4-methyl-B-thiomorpholinone 20% sodium lininsulfonate 5% powdere attapulgite clay 75% To prepare the aboveformulation the ingredients can be blended and moistened with water toproduce a product suitable for pelletizing. This wet material ispelletized and dried.

The pellets so prepared can be sprinkled at the rate of 5 kg (activeingredient) per 4,000 meters of row in the furrow when plantingcucumbers. The seeds then can be planted and the furrow closed. Thecucumbers will grow free of attack by the root knot nematode,Meloidogyne incognita.

EXAMPLE High Strength Concentrate2-methylcarbarnoyloxyimino-4-methyl-3-thiomorpholinone 97% silicaaerogel l% synthetic amorphous fine silica 1% anhydrous magnesiumsulfate 1% To prepare the above formulation the ingredients can beblended and ground to produce a material which will essentially all passthrough a U.S.S. No. 50 mesh screen (0.3 mm openings). This material canbe shipped or formulated in a number of ways. For example, the following25% dust can be prepared.

high strength concentrate pyrophyllite The materials can be thoroughlyblended and packaged for use.

This formulation can be applied with conventional dust equipment to afield of tomatoes at the rate of l .5 5 kg of active ingredient perhectare, a total of four applications are made during the season. Suchtreatment will give excellent control of the southern armyworm (Prodem'aeridania).

10 EXAMPLE l6 Agueous Suspension2-methylcarbamoyloxyimine-4-methyltetrahydro l ,44hiazepin-3-one 25.00%i 5 sodium ligninsulfonate 6.00% hydrated attapulgite 2.00% sodiumdihydrogen phosphate [00% phenyl mercury acetate 025% water 65.75%

In preparing the above formulation, the ingredients can be combined andsand milled to produce particles substantially all below 2 microns.

A 1% (active ingredient) suspension of this formulation can be preparedin 100 liters of water and the resulting suspension can be used forspraying the walls, floor and stalls of a barn for the control of houseand stable flies.

I claim:

1. A compound of the formula:

0 Re I l 5 N i1 O N- 41,;

l in where R; is hydrogen, alkyl of l-6 carbon atoms, alkenyl of 34carbon atoms, or alkynyl of 3-4 carbon atoms; R is hydrogen, alkyl ofl-3 carbon atoms, or allyl; R is hydrogen or methyl; and

n is 3-4. 2. A compound of the formula:

HON ll-R;

where R, is hydrogen, alkyl of l-6 carbon atoms, alkenyl of 3-4 carbonatoms, or alkynyl of 3-4 carbon atoms; and n is 3-4.

1. A COMPOUND OF THE FORMULA
 2. A COMPOUND OF THE FORMULA: